Automated Characterization of a Diesel Sample Using

®
Automated Characterization of a Diesel Sample Using
Comprehensive Two-Dimensional GC (GCxGC) and
Time-of-Flight Mass Spectrometry (TOFMS) Detection
(Pegasus® 4D System)
LECO Corporation; Saint Joseph, Michigan USA
Key Words: GCxGC-TOFMS, Petroleum, Classifications
3. Results
One of the advantages of using GCxGC for
chromatographic separation is the high degree of
organization based on chemical structure that can be seen
in the resulting chromatogram. Components from the
same class are aligned in bands based on the two
separation mechanisms used. This can be seen in Figure 1
where the total ion current (TIC) chromatogram of the
diesel sample is displayed as a surface plot, and also in the
contour plot displayed in Figure 2.
Components that elute from the first column of a GCxGC
system are thermally modulated and sharp eluent pulses
enter the second column of the system. This results in very
narrow chromatographic peaks that have to be
characterized after elution from the secondary column,
and consequently fast data acquisition systems are
needed for detection. LECO's Pegasus TOFMS is the only
mass spectrometer capable of acquisition rates of 500 full
spectra/second, adequate for the detection of peaks as
narrow as 20 msec.
The purpose of the analysis was a diesel sample obtained
before removal of sulfur-containing components was
analyzed for chemical class pattern identification.
2. Experimental Conditions
GCxGC:
Agilent 6890 GC equipped with a LECO Thermal
Modulator (Technology under license from Zoex Corporation)
Primary Column:
DB-PONA, 50 m, 0.2 mm id, 0.5 µm film thickness
Main Oven:
100°C (0.2 minute hold) to 240°C (66.7 minute hold)
at 1.5°C/minute
Secondary Column:
DB-WAX, 2 m, 0.1 mm id, 0.1 µm film thickness
Secondary Oven:
110°C (1 minute hold) to 240°C (74.5 minute hold)
at 1.5°C/minute
Inlet Temp:
250°C
Injection Size:
0.2µl
Split Ratio:
100:1
Carrier Gas:
He at a constant flow of 1.5 ml/minute
Modulator Temp:
30ºC offset from main oven
Modulation Frequency:
5 seconds with a 0.6 second hot pulse time
Figure 1. TIC chromatogram of a diesel sample prior to removal of the
sulfur-containing components.
In Figure 2, chemical structures for groups of components
present in different regions of the chromatogram are
presented. As can be seen in this figure, the
chromatogram is organized by carbon number in the first
dimension (primary non-polar column), and by polarity in
the second dimension (secondary polar column).
S
(CH3)2
CH3
CH3
(CH3)2
(CH3)3
S
CH3
O
(CH3)3
O
S
(CH3)2
(CH3)2
CH3
S
S
(CH3)2
S
CH3
S
CH3
(CH3)2
(CH3)4
S
CH3
(CH3)4
S
CH3
S
(CH3)4
(CH3)3
(CH3)2
S
C24H50
C24
S
MS:
Ionization:
Mass Range (u):
Acquisition Rate:
Source Temp:
®
LECO Pegasus 4D GCxGC-TOFMS
EI at 70eV
35 to 500
100 spectra/second
225ºC
C23H48
C23
S
(CH3)2
C15
C15H32
C16
C16H34
CH3
H3C
(CH3)2
(CH3)3
(CH3)4
(CH3)5
(CH3)2
CH3
C19H40
C19
C18
C18H38
C17
C17H36
CH3
CH3
CH3
H3C
CH3
CH3
CH3
C20H42
C20
C21H44
C21
C22H46
C22
CH3
CH3
(CH3)3
(CH3)6
Figure 2. TIC chromatogram of the diesel sample presented as a contour plot.
Chemical structures for different classes of components are also presented.
Structures for sulfur-containing components are drawn in yellow for better
visualization.
Life Science and Chemical Analysis Solutions
1. Introduction
The high complexity of diesel samples makes them good
candidates for two-dimensional comprehensive gas
chromatography (GCxGC). In addition to the challenge
created by the presence of thousands of components,
each of the analytes is of importance to the petroleum
industry and cannot be treated as interference. The need
for complete characterization of the analytes has led to an
increase in the interest of coupling mass spectrometry to
GCxGC systems.
Delivering the Right Results
As the structural complexity of the components increases,
partial overlap for component classes can be seen even
though GCxGC offers a tremendous increase in peak
capacity. This can be easily resolved when a mass
spectrometer is used for detection. An example is
presented in Figure 3, which represents the region
surrounded by a dashed line in Figure 2 on a smaller
scale. Plotting unique m/z values for the different
structural classes allows the analysts to identify three
different classes when only one class seemed to be
present in the TIC chromatogram.
(a)
(b)
(c)
(d)
Figure 4. (a) TIC chromatogram for the diesel sample with peak markers for
the found peaks represented as black dots. A selected region of the
chromatogram for which a sum of m/z is shown is presented on a reduced
scale as a contour plot (b) and as a surface plot (c). Chemical structures for
the components of interest are also presented in part (b) of the figure.
Figure 3. Reduced scale of the substituted benzothiophene (red line),
substituted biphenyl (blue line), and substituted naphthalene (white line)
region from Figure 2. TIC (a), as well as characteristic m/z values for C12
benzothiophene (b), C14 biphenyls (c), and C14 naphthalenes (d), are shown
in the same region of the chromatogram.
®
More than 6,000 components were found to be present in
the diesel sample when acquired data was processed at a
S/N value of 500. Figure 4 shows an example of a region
of the chromatogram where the found peaks do not
appear to be actual peaks. This is caused by higher
intensity peaks scaling the chromatogram and making the
lower intensity peaks to be almost lost into the blue
background. By plotting the sum of the unique ions for the
peaks of interest, their appearance can be greatly
enhanced. The black dots in parts (a) and (b) of the figure
represent peak markers for the found peaks.
4. Conclusions
Comprehensive two-dimensional GC (GCxGC) provided
the additional peak capacity necessary to resolve more
than 6,000 components present in the diesel sample. The
highly organized chromatogram based on chemical
structure added more power to component identification
by providing confirmation for the results obtained from the
mass spectral data. On the other hand, the addition of
TOFMS detection to GCxGC technique proved to be a
powerful tool in solving class identification for regions of
the chromatograms where two or more chemical classes
of components overlapped. In conclusion, GCxGC and
TOFMS are complementary, allowing complete and
automated characterization of the complex diesel sample.
LECO Corporation • 3000 Lakeview Avenue • St. Joseph, MI 49085 • Phone: 800-292-6141 • Fax: 269-982-8977
info@leco.com • www.leco.com • ISO-9001:2000 • No. FM 24045 • LECO is a registered trademark of LECO Corporation.
Form No. 203-821-230
4/08-REV1
© 2008 LECO Corporation